Ta Clusters Research Articles

Selective Reduction of NO into N2 Catalyzed by the RhM2O3- Clusters (M = Ta, V, and Al): Importance of the Triatomic Lewis Acid-Base-Acid Mδ+-Rhδ--Mδ+ Site.

Catalytic NO reduction by CO into N2 and CO2 is imperative owing to the increasingly rigorous emission regulation. Identifying the nature of active sites that govern the reactivity and selectivity of NO reduction is pivotal to tailor catalysts, while it is extremely challenging because of the complexity of real-life systems. Guided by our newly discovered triatomic Lewis acid-base-acid (LABA, Ceδ+-Rhδ--Ceδ+) site that accounts for the selective reduction of NO into N2 catalyzed by the RhCe2O3- cluster in gas-phase experiments, the reactivity of the RhM2O3- (M = Ta, V, and Al) clusters in catalytic NO reduction by CO was explored. We determined theoretically that the LABA site still prevails to reduce NO to N2 mediated by RhTa2O3- and RhV2O3-, and the strong M-oxygen affinity was emphasized to construct the LABA site. An overall assessment highlights that RhV2O3- functions as a more promising catalyst because the well-fitting V-O bonding strength facilitates both elementary reactions of NO reduction and CO oxidation.

Performance of density-functional-theory and random-phase-approximation methods on the study of transition-metal clusters: the Tan clusters as an example

Recently developed density-functional-theory (DFT) and random-phase-approximation (RPA) methods are used to study competing isomers of some negatively charged Ta clusters, namely Ta12 - and Ta10 -, in an attempt to find a suitable strategy towards accurate studies of transition-metal clusters based on DFT. Also the neutral and cationic forms Ta12 (0,+) of the twelve-atom cluster are studied. The results are compared with experimental information obtained by several methods that differ in the property under study and the total electric charge of the clusters. We find that a careful choice of the density functional, the use of relativistic two-component methods, eventually in combination with all-electron basis sets, and the application of RPA-type methods, may all be necessary steps for a good assessment. Such an assessment should be made in relation to several experimental properties as much as possible.

Oxidation behavior and atomic structural transition of size-selected coalescence-resistant tantalum nanoclusters

Herein a series of size-selected Ta N (N = 147, 309, 561, 923, 1415, 2057, 6525, 10 000, 20 000) clusters are generated using a gas-phase condensation cluster beam source equipped with a lateral time-of-flight mass-selector. Aberration-corrected scanning transmission electron microscopy (AC-STEM) imaging reveals good thermal stability of Ta N clusters in this study. The oxidation-induced amorphization is observed from AC-STEM imaging and further demonstrated through x-ray photoelectron spectroscopy and energy-dispersive spectroscopy. The oxidized Ta predominantly exists in the +5 oxidation state and the maximum spontaneous oxidation depth of the Ta cluster is observed to be 5 nm under prolonged atmosphere exposure. Furthermore, the size-dependent sintering and crystallization processes of oxidized Ta N clusters are observed with an in situ heating technique, and eventually, ordered structures are restored. As the temperature reaches 1300 °C, a fraction of oxidized Ta309 clusters exhibit decahedral and icosahedral structures. However, the five-fold symmetry structures are absent in larger clusters, instead, these clusters exhibit ordered structures resembling those of the crystalline Ta2O5 films. Notably, the sintering and crystallization process occurs at temperatures significantly lower than the melting point of Ta and Ta2O5, and the ordered structures resulting from annealing remain well-preserved after six months of exposure to ambient conditions.

Coalescence behavior of size-selected gold and tantalum nanoclusters under electron beam irradiation: insights into nano-welding mechanisms.

The emerging technique of nano-welding (NW) via precisely regulating the fusion of nanoclusters (NCs) in nanotechnology has attracted significant attention for its innovative approach. Employing the gas-phase condensation cluster source with a lateral time-of-flight (TOF) mass-selector, size-selected gold (Au), and tantalum (Ta) NCs were prepared. This study explores the coalescence behavior of size-selected Au and Ta NCs under electron beam irradiation, aiming to investigate the related mechanism governing the welding process. Intrinsically driven by the reduction of excess surface energy, electron beam induces atomic thermal migration, fostering sintering neck growth at cluster interfaces. During this process, atomic diffusion and recrystallization enable NCs to alter shape while retaining stable facet planes. Aberration-corrected scanning transmission electron microscopy (AC-STEM) showcases the formation of single or polycrystalline sintered clusters, during which some lattice distortions can be eliminated. Interestingly, oxidized Ta clusters experience knock-on damage caused by elastic scattering of electron beams, partially deoxidizing them. Additionally, electron-phonon inelastic scattering transforms oxidized Ta clusters from amorphous to crystalline structures. Moreover, the quantum size effect and surface effect of NCs facilitate the surpassing of miscibility limits during Au-Ta heterogeneous welding processes. This investigation bridges the gap between fundamental research on cluster materials and their practical applications.

Cryo-IR spectroscopy and cryo-kinetics of cluster N2 adsorbate complexes of tantalum cluster cations Ta5-8.

We present an IR-PD study of tantalum cluster adsorbate complexes [Tan(N2)m]+, abbreviated (n,m), n = 5-8. We utilize infrared spectroscopy of isolated and size selected clusters as prepared and characterized by a cryogenic tandem ion trap setup, and we augment our experiments with quantum chemical simulations at the level of density functional theory. The cluster adsorbate complexes (n,m) reveal vibrational bands above 2000cm-1, which indicate end-on coordinated μ1-N2 oscillators, and bands below 2000cm-1, which indicate side-on μ2-κN:κN,N coordinated ones. We observe a general increase in spectral complexity and an inhomogeneous broadening, mainly towards the red, at certain points of N2 loading m, which originates from an increasingly higher amount of double and triple N2 coordination at Ta sites, eventually at all of them. Other than the small tantalum clusters Tan+, n = 2-4, the IR-PD spectra of the initial N2 adsorbate species (n,1), n = 5-8, provide strong evidence for a lack of spontaneous N2 cleavage. Spontaneous N2 cleavage by Tan+, n = 5-8, seems suppressed. Therefore, the ability of a small Ta cluster to cleave dinitrogen disappears with one more tantalum core atom. The study of stepwise N2 adsorption on size selected Tan+, n = 5-8 clusters revealed adsorption limits m(max) of [Tan(N2)m]+ that are independent of cluster size within this size range. Cryo-adsorption kinetics at 26K allowed for kinetic fits to consecutive N2 adsorption steps, and the fits revealed significant N2 desorption rates upon higher N2 loads, and the cluster adsorbate complexes eventually reached equilibrium. Some enhanced N2 desorption rates point towards likely adsorbate shell reorganization, and there is also some evidence for the coexistence of isomeric cluster adsorbate complexes.

Shed light on new growth pattern in rapid solidified Ta metal: MD simulation, DFT calculation and CALYPSO search

Aiming at the micro-structures of rapid solidified Ta system under cooling rate of 1×1010 K/s, the lowest-energy and meta-stable geometric structure of Tan (n = 19–30) clusters are systematically investigated via MD simulation, DFT calculation and CALYPSO search. It is revealed that the ground-state geometric structure of free Ta clusters plays a significant role in determining its solidified atomic structures and evolution laws in the early stage of nucleation. We explained why the hexagonal close packed (hcp) atomic clusters (Ta22) dominate the solid state of Ta when cooled at a rate of 1 × 1010 K/s. And found that the coexistence of slightly distorted icosahedral (Ta13) and hcp clusters (Ta22) at 300 K is due to the high energy stability of free Ta26–C2v (B) cluster. The larger size of Ta clusters with a perfect closed-shell geometric structure plays a key role in energetic effects, as demonstrated by their thermodynamic stability in terms of binding energy. Additionally, electronic structure stability is achieved when there are fewer electrons on the Fermi level (N(EF)), resulting in Ta atomic clusters that exhibit higher energetic stability and lower chemical activity. Our analysis of the interaction between different atoms in Ta clusters revealed that stronger electronic interactions of central(c)-central(c) and central(c)-shell(s) atoms contribute to the higher energy and chemical stability. Finally, we provide insights into understanding the growth patterns of nucleation in liquid metals through an examination of geometric and electronic structures of free Ta cluster.

73-OR: Multiancestry Genetic Clustering of Type 2 Diabetes Loci Highlights the Contribution of Non-European Variants to Disease Heterogeneity

To identify potential subtypes of type 2 diabetes (T2D) anchored in genetics but informed by physiology, we previously used a soft clustering method to cluster T2D single nucleotide variants (SNVs) by their associated metabolic traits. The resulting European-based clusters represent likely disease mechanistic pathways. However, ancestry-specific SNVs, phenotype characteristics and prevalence rates suggest that a portion of the T2D’s heterogeneity is population-based, requiring expansion of this work to non-European populations. We created a semi-automated Bayesian non-negative matrix factorization (bNMF) pipeline to generate new ancestry-specific clusters in European (EUR, 390 SNVs), East Asian (EAS, 326 SNVs) and African (AFR, 172 SNVs), as well as trans-ancestry (TA, 498 SNVs), using up to 89 T2D-related traits. We validated the clusters by replicating their trait associations in the Mass General Brigham Biobank cohort (MGBB, N=62,252). The new ancestry-specific and TA clusters captured previously identified clusters, as well as novel clusters related to possible mechanisms of insulin resistance. In the 11 TA clusters, 127/498 SNVs were from non-EUR T2D studies, with 87 SNVs not represented in the EUR clusters. In the non-European subset of MGBB (N=8,990), 8 of 10 TA cluster pPS were more strongly associated with T2D compared to the corresponding EUR cluster pPS. We assessed in MGBB whether the proportion of cumulative genetic risk attributed to each cluster differed between sub populations. A significantly higher proportion was attributed to the Lipodystrophy cluster in EAS, to the Obesity cluster in EUR, and to the Liver/Lipid cluster in AFR (all t-test P<10-15). By expanding our previous clusters to include non-European SNVs, we were able to identify new genetic clusters and improve the predictive ability of cluster pPS. Our results suggest that polygenic processes contribute in different proportions across populations. Disclosure K.Smith: None. A.Manning: None. J.M.Mercader: None. M.Udler: None. H.Kim: None. K.E.Westerman: None. S.Hsu: None. R.Mandla: None. P.H.Schroeder: None. T.Majarian: Employee; Vertex Pharmaceuticals Incorporated. V.Kaur: None. J.C.Florez: Consultant; AstraZeneca, Novo Nordisk, Other Relationship; AstraZeneca, Merck & Co., Inc. Funding National Institute of Diabetes and Digestive and Kidney Diseases (R03DK131249)

Heteronuclear Trimetallic MFe2 and M2 Fe (M=V, Nb, and Ta) Clusters for Dinitrogen Activation.

Catalysts with heteronuclear metal active sites may have high performance in the nitrogen reduction reaction (NRR), and the in-depth understanding of the reaction mechanisms is crucial for the design of related catalysts. In this work, the dissociative adsorption of N2 on heteronuclear trimetallic MFe2 and M2 Fe (M=V, Nb, and Ta) clusters was studied with density functional theory calculations. For each cluster, two reaction paths were studied with N2 initially on M and Fe atoms, respectively. Mayer bond order analysis provides more information on the activation of N-N bonds. M2 Fe is generally more reactive than MFe2 . The coordination mode of N2 on three metal atoms can be end-on: end-on: side-on (EES) for both MFe2 and M2 Fe. In addition, a unique end-on: side-on: side-on (ESS) coordination mode was found for M2 Fe, which leads to a higher degree of N-N bond activation. Nb2 Fe has the highest reactivity towards N2 when both the transfer of N2 and the dissociation of N-N bonds are taken into account, while Ta-containing clusters have a superior ability to activate the N-N bond. These results indicate that it is possible to improve the performance of iron-based catalysts by doping with vanadium group metals.

Base Catalysis of Sodium Salts of [Ta6−xNbxO19]8− Mixed-Oxide Clusters

The solid base catalysis of sodium salts of Lindqvist-type metal oxide clusters was investigated using a Knoevenagel condensation reaction. We successfully synthesized the sodium salts of Ta and Nb mixed-oxide clusters Na8−nHn[(Ta6−xNbx)O19]·15H2O (Na-Ta6−xNbx, n = 0, 1, x = 0–6) and found them to exhibit activity for proton abstraction from nitrile substrates with a pKa value of 23.8, which is comparable to that of the conventional solid base MgO. The Ta-rich Na-Ta6 and Na-Ta4Nb2 exhibited high activity among Ta and Nb mixed-oxide clusters. Synchrotron X-ray diffraction (SXRD) measurements, Fourier-transform infrared (FT-IR) spectroscopy, and X-ray absorption spectroscopy (XAS) revealed the structure of Na-Ta6−xNbx: (1) The crystal structure changed from Na7H[M6O19]·15H2O to Na8[M6O19]·15H2O (M = Ta or Nb) by the anisotropic expansion of the unit cell with an increase in Ta content; (2) Highly symmetrical Lindqvist [Ta6−xNbxO19]8− was generated in Na-Ta4Nb2 and Na-Ta6 because of the symmetrical association of Na+ ions with [Ta6−xNbxO19]8− in the structure. DFT calculation revealed that the Lindqvist structures with high symmetry have large NBO charges on surface oxygen species, which are strongly related to base catalytic activity, whereas the composition hardly affects the NBO charges. The above results showed that the Brønsted base catalysis was sensitive to the symmetry of the Lindqvist [Ta6−xNbxO19]8− structure. These findings contribute to the design of solid base catalysts composed of anionic metal oxide clusters with alkaline-metal cations.

Influence of Nitrogen Adsorption of Doped Ta on Characteristics of SiNx‐Based Resistive Random Access Memory

The characteristics and conductive mechanism of Ta/SiNx/Ta:SiNx/SiNx/Pt resistive random access memory (RRAM) are investigated. Compared with Pt‐doped devices with the same structure, the Ta‐doped devices produce lower operation current in a high resistance state and a larger on/off radio. Furthermore, reliability tests show that the Ta‐doped RRAM has good data retention ability and endurance. Ta clusters are observed in the Ta‐doped SiNx layer through the transmission electron microscope. Also, the X‐ray photoelectron spectra indicate that additional Si dangling bonds and tantalum nitride are present in the Ta‐doped SiNx film. Based on the structure of the device, material analysis, and electrical characteristics, a model is proposed to explain the influence of the doped Ta on resistive switching behavior of the device.

Nanoscale potential fluctuations in nonstoichiometrics tantalum oxide

The atomic and electronic structure of nonstoichiometric amorphous tantalum oxide (TaOx) films of different composition has been investigated by means of electron microscopy, x-ray photoelectron spectroscopy, Raman and infrared spectroscopy. The dispersion of the absorption coefficient and refraction index has been studied by spectral ellipsometry. The optical spectra were interpreted using the results of a quantum-chemical simulation for crystalline orthorhombic TaOx. It was found that the presence of oxygen vacancies in the oxygen-deficient TaOx film show an optical absorption peak at 4.6 eV. It has been established that TaOx consists of stoichiometric Ta2O5, metallic Ta clusters less than 20 nm in size, and tantalum suboxides TaOy (y < 2.5). The model of nanoscale potential fluctuations of TaOx bandgap in the range of 0–4.2 eV is proposed and justified. The design of the flash memory element based on the effect of localization of electrons and holes in Ta metallic nanoclusters in the TaOx matrix is proposed.

Kramers degeneracy and relaxation in vanadium, niobium and tantalum clusters

In this work we use magnetic deflection of V, Nb, and Ta atomic clusters to measure their magnetic moments. While only a few of the clusters show weak magnetism, all odd-numbered clusters deflect due to the presence of a single unpaired electron. Surprisingly, for the majority of V and Nb clusters an atomic-like behavior is found, which is a direct indication of the absence of spin–lattice interaction. This is in agreement with Kramers degeneracy theorem for systems with a half-integer spin. This purely quantum phenomenon is surprisingly observed for large systems of more than 20 atoms, and also indicates various quantum relaxation processes, via Raman two-phonon and Orbach high-spin mechanisms. In heavier, Ta clusters, the relaxation is always present, probably due to larger masses and thus lower phonon energies, as well as increased spin–orbit coupling.

Atomistic modeling of capillary-driven grain boundary motion in Cu-Ta alloys

Nanocrystalline Cu-Ta alloys are emerging as a new class of structural materials preserving the nano-scale grain size up to the melting point of Cu. This extraordinary structural stability is caused by the strong pinning of grain boundaries (GBs) by Ta nano-clusters precipitating from the unstable solid solution after mechanical alloying. Many aspects of the Ta stabilization effect remain elusive and call for further experimental and simulation work. In previous atomistic computer simulations of stress-driven GB migration [JOM68, 1596 (2016)], the GB–cluster interactions in Cu-Ta alloys have been studied for several different compositions and GB velocities. The results have pointed to the Zener pinning as the main mechanism responsible for the grain stabilization. This paper extends the previous work to the motion of individual GBs driven by capillary forces whose magnitude is similar to that in real nanocrystalline materials. Both the impingement of a moving GB on a set of Ta clusters and the GB unpinning from the clusters are studied as a function of temperature and alloy composition. The results demonstrate a quantitative agreement with the Zener pinning model and confirm the “unzip” mechanism of unpinning found in the previous work. In the random Cu-Ta solid solution, short-circuit Ta diffusion along stationary and moving GBs leads to the nucleation and growth of new GB clusters, which eventually stop the GB motion.

Role of nanoscale Cu/Ta interfaces on the shock compression and spall failure of nanocrystalline Cu/Ta systems at the atomic scales

Molecular dynamics (MD) simulations are used to investigate the role of size and distribution of nanoscale Cu/Ta interfaces on the nucleation and evolution of defects during shock loading and spall failure of nanocrystalline (nc) Cu/Ta alloys. Cu/Ta interfaces are introduced through the embedding of Ta clusters in nc-Cu matrix. The phase stability of the embedded Ta clusters either as FCC or BCC clusters is first investigated and reveals that the FCC Ta clusters have a lower energy for diameters less than 4 nm, whereas the BCC Ta clusters have a lower energy for the larger diameters. The shock simulations are then carried out for Ta clusters with an average diameter of 1 and 3 nm and concentrations of 3.0, 6.3 and 10.0% to investigate the role of size and distribution of Cu/Ta interfaces (due to presence of clusters) on the nucleation and evolution of dislocations as well as the spall strength of the alloy. The MD simulations indicate that the Cu/Ta interfaces reduce the capability of nc-Cu to accommodate plasticity through nucleation of dislocations and create void nucleation sites during spallation. The MD simulations further reveal that the impact strengthening effects due to the presence of nanoscale Cu/Ta interfaces are strongly dependent upon the size and distribution of Ta clusters, as well as the grain size of Cu matrix. Smaller size of interfaces (cluster size), higher concentration of Ta (smaller spacing between interfaces) and larger matrix grain size render higher spall strengths of nc-Cu/Ta microstructures.

Microstructural evolution in a nanocrystalline Cu-Ta alloy: A combined in-situ TEM and atomistic study

Under intense heating and/or deformation, pure nanocrystalline (NC) metals exhibit significant grain coarsening, thus preventing the study of length scale effects on their physical response under such conditions. Hence, in this study, we use in-situ TEM heating experiments, atomistic modeling along with elevated temperature compression tests on a thermally stabilized nanostructured Cu–10at.% Ta alloy to assess the microstructural manifestations caused by changes in temperature. Results reveal the thermal stability attained in NC Cu-10at.% Ta diverges from those observed for conventional coarse-grained metals and other NC metals. Macroscopically, the microstructure, such as Cu grain and Ta based cluster size resists evolving with temperature. However, local structural changes at the interface between the Ta based clusters and the Cu matrix have a profound effect on thermo-mechanical properties. The lattice misfit between the Ta clusters and the matrix tends to decrease at high temperatures, promoting better coherency. In other words, the misfit strain was found to decrease monotonically from 12.9% to 4.0% with increase in temperature, leading to a significant change in flow stress, despite which (strength) remains greater than all known NC metals. Overall, the evolution of such fine structures is critical for developing NC alloys with exceptional thermo-mechanical properties.

Probing the coupling between a doublon excitation and the charge-density wave inTaS2by ultrafast optical spectroscopy

Recently, the switching between the different charge-ordered phases of $1T\ensuremath{-}{\mathrm{TaS}}_{2}$ has been probed by ultrafast techniques, revealing unexpected phenomena such as ``hidden'' metastable states and peculiar photoexcited charge patterns. Here, we apply broadband pump-probe spectroscopy with varying excitation energy to study the ultrafast optical properties of $1T\ensuremath{-}{\mathrm{TaS}}_{2}$ in the visible regime. By scanning the excitation energy in the near-IR region we unravel the coupling between different charge excitations and the low-lying charge-density wave state. We find that the amplitude mode of the charge-density wave exhibits strong coupling to a long-lived doublon state that is photoinduced in the center of the star-shaped charge-ordered Ta clusters by the near-IR optical excitation.

Nitrogen Molecule Adsorption on Cationic Tantalum Clusters and Rhodium Clusters and Desorption from Their Nitride Clusters Studied by Thermal Desorption Spectrometry.

Adsorption and desorption of N2 molecules onto cationic Ta and Rh clusters in the gas phase were investigated in the temperature range of 300-1000 K by using thermal desorption spectrometry in combination with density functional theory (DFT) calculations. For Ta6(+), the first N2 molecule was found to adsorb dissociatively, and it remained adsorbed when Ta6(+)N2 was heated to 1000 K. In contrast, the second and the subsequent N2 molecules adsorbed weakly as a molecular form and were released into the gas phase when heated to 600 K. The difference can be explained in terms of the activation barrier between the molecular and dissociative forms. On the other hand, when Ta clusters were generated in the presence of N2 gas by the laser ablation of a Ta rod, isomeric clusters, TanNm(+), having heat resistivity were formed. For Rh6(+), N2 adsorbed molecularly at 300 K and desorbed totally at 450 K. These results were consistent with the DFT calculations, indicating that the dissociative adsorption of N2 is endothermic.

Zener Pinning of Grain Boundaries and Structural Stability of Immiscible Alloys

Immiscible Cu-Ta alloys produced by mechanical alloying are currently the subject of intensive research due to their mechanical strength combined with extraordinary structural stability at high temperatures. Previous experimental and simulation studies suggested that grain boundaries (GBs) in Cu-Ta alloys are stabilized by Ta nano-clusters coherent with the Cu matrix. To better understand the stabilization effect of Ta, we performed atomistic computer simulations of GB–cluster interactions in Cu-Ta alloys with various compositions and GB velocities. The study focuses on a single plane GB driven by an applied shear stress due to the shear-coupling effect. The results of the simulations are in close quantitative agreement with the Zener model of GB pinning. This agreement and the large magnitude of the unpinning stress confirm that the structural stability of these alloys is due to the drastically decreased GB mobility rather than a reduction in GB energy. For comparison, we simulated GB motion in a random solid solution. While the latter also reduces the GB mobility, the effect is not as strong as in the presence of Ta clusters. GB motion in the random solution itself induces precipitation of Ta clusters due to short-circuit diffusion of Ta in GBs, suggesting a possible mechanism of cluster formation inside the grains.

Effect of Ta Solute Concentration on the Microstructural Evolution in Immiscible Cu-Ta Alloys

The immiscible Cu-Ta system has garnered recent interest due to observations of high strength and thermal stability attributed to the formation of Ta-enriched particles. This work investigated a metastable Cu-1 at.% Ta solid solution produced via mechanical alloying followed by subsequent consolidation into a bulk specimen using equal channel angular extrusion at 973 K (700°C). Microstructural characterization revealed a decreased number density of Ta clusters, but with an equivalent particle size compared to a previously studied Cu-10 at.% Ta alloy. Molecular dynamic stimulations were performed to understand the thermal evolution of the Ta clusters. The cluster size distributions generated from the simulations were in good agreement with the experimental microstructure.

Structure and thermal decomposition of a nanocrystalline mechanically alloyed supersaturated Cu–Ta solid solution

Abstract